Electonic Supplementy Mteil (ESI) fo Physicl Chemisty Chemicl Physics. This jounl is The Royl Society of Chemisty 2014 Suppoting Infomtion fo: Pedicting phosphoescent lifetimes nd zeo-field splitting of ognometllic complexes with time-dependent density functionl theoy including spin-obit coupling K. Moi, T. P. M. Goumns, b E. vn Lenthe b nd F. Wng c Ryok Systems Inc., Science nd Technology Systems Division, Tokyo Skytee Est Towe 1-1-2, Oshige, Sumid-ku, Tokyo 131-0045, Jpn, moi@si.co.jp b Scientific Computing & Modelling NV, Vije Univesiteit, Theoeticl Chemisty, De oeleln 1083, 1081 HV Amstedm, The Nethelnds c College of Chemisty, Sichun Univesity, 24, South Section 1, Yihun Rod, Chengdu, 610064 Sichun, P. R. Chin Contents p. 2 Tble S1. Clculted ZFS nd ditive lifetime τ t the 4 levels of theoy, petubtive o full SOC, gs phse o COSMO solvtion. p. 3 Tble S2. CPU timings fo I(ppy) 3 clcultions t the 4 levels of theoy, petubtive o full SOC, gs phse o COSMO solvtion. p. 4 Tble S3. Clculted ZFS nd ditive tes nd lifetimes fo I(ppy) 3 with (p) comped with pevious theoeticl studies nd expeimentl dt. p. 5 Figue S1. Clculted ZFS nd τ t the COSMO + level fo sevel I(N^C) 2 (cc) nd Pt(N^C)(cc) compounds, comped to expeimentl dt. p. 6 Figue S2. Clculted ZFS nd τ t the 4 levels of theoy (petubtive o full SOC, gs phse o COSMO solvtion), comped to expeimentl dt. p. 7 Refeences 1
Tble S1. Clculted ZFS (cm -1 ) nd ditive lifetime τ (s) t the 4 levels of theoy, petubtive o full SOC, gs phse o COSMO solvtion. No. Compound Symmety E(ZFS) (300K) Gs COSMO Gs COSMO 1 [Rh(bpy) 3 ] 3+ C 2 0.2 0.2 0.2 0.1 2.9E+03 1.5E+04 3.7E+03 5.6E+03 2 [I(bpy) 3 ] 3+ C 2 5.5 1.9 5.6 1.6 181.0 167.0 171.8 87.1 3 Pd(thpy) 2 C 1 3.4 2.3 1.9 0.9 302.5 574.7 221.7 287.8 4 Pt(s1-thpy)(cc) C 1 8.0 9.3 4.2 4.5 95.5 104.8 103.7 47.5 5 Re(pbt)(CO) 4 C 1 2.4 3.2 1.4 1.3 125.2 124.4 180.4 78.0 6 Pt(thpy)(cc) C 1 16.3 12.1 11.0 5.8 90.2 87.7 100.2 38.7 7 Pt(4,6-dFpthiq)(dpm) C 1 32.6 24.6 15.7 9.7 34.1 28.5 39.4 14.3 8 Pt(4,6-dFppy)(cc) C 1 48.4 36.3 24.7 14.9 37.6 30.9 38.4 11.3 9 Pt(pbt)(cc) C 1 38.7 28.6 21.5 13.1 36.0 47.1 32.0 15.9 10 Pt(thpy) 2 C 1 36.8 35.6 17.7 13.6 7.8 57.8 18.8 20.0 11 I(s1-thpy) 2 (cc) C 2 25.9 35.7 29.8 34.5 9.2 25.0 9.4 10.1 12 I(btp) 2 (cc) C 1 26.2 20.7 18.4 17.7 51.1 61.7 44.0 25.4 13 I(thpy) 2 (cc) C 2 52.7 40.9 51.1 38.0 12.8 22.1 12.2 8.0 14 I(4,6-dFppy) 2 (pic) C 1 71.5 98.6 42.1 53.6 14.9 7.4 14.4 3.2 15 I(piq) 3 C 1 74.4 114.4 55.8 71.8 9.6 7.1 14.1 3.4 16 [Ru(bpy) 3 ] 2+ C 2 88.6 125.3 90.3 122.0 29.7 14.6 20.0 4.9 17 I(biq) 3 C 1 101.1 150.6 87.7 118.2 3.4 3.2 3.7 1.5 18 I(piq) 2 (cc) C 1 111.1 148.9 81.1 95.7 12.8 7.7 15.9 3.4 19 I(pbt) 2 (cc) C 1 170.7 220.8 148.2 181.0 6.6 8.2 5.8 2.8 20 I(4,6-dFppy) 2 (cc) C 1 107.3 143.8 101.0 124.0 6.8 5.4 4.7 1.9 21 I(dm-2-piq) 2 (cc) C 2 98.3 157.5 112.1 134.7 7.6 3.7 6.2 1.1 C 1 n/ n/ 146.5 168.3 n/ n/ 9.1 2.1 22 I(ppy) 3 C 1 101.8 143.6 83.6 105.3 7.5 5.6 5.5 2.1 23 [Os(bpy) 3 ] 2+ D 3 148.9 217.9 153.2 180.7 2.1 2.0 2.1 0.6 C 2 n/ n/ 559.9 690.5 n/ n/ 11.0 5.9 bbevition fo lignds sme s in min ppe. 2
Tble S2. CPU timings (s) fo I(ppy) 3 clcultions t the 4 levels of theoy, petubtive o full SOC, gs phse o COSMO solvtion. Gs COSMO No. of excittions b 20 (10/10) 40 (20/20) 4 20 (10/10) 40 (20/20) 4 No. of itetions c 15 (6/9) 16 (7/9) 11 15 (6/9) 20 (11/9) 11 Totl CPU time 22870 47362 57637 23262 60431 78147 CPU time/ itetion 1525 2960 5240 1551 3022 7104 Clcultions wee un on dul hex coe Intel(R) Xeon(R) CPU E5-2620 @ 2.00GHz. b The numbes of singlet nd tiplet excittion used in e epoted within pentheses s (singlet/tiplet). c The numbes of itetions which wee needed fo singlet nd tiplet excittions in e epoted within pentheses s (singlet/tiplet). While the computtionl effot of is bout ten times smlle thn tht of fo given numbe of excittions, 1 the psoc ppoch uses tuncted spce fo the petubtion expnsion, nd consequently moe excittions e needed fo bette desciption of the spin-mixed excittions obtined in. Fo the choice of 40 (20 singlet + 20 tiplet) excittions in, which wee used in min ppe, the gin in computtionl efficiency ove with 4 spin-mixed excittions is educed. 3
Tble S3. Clculted ZFS (cm -1 ) nd ditive tes (s -1 ) nd lifetimes (s) fo I(ppy) 3 with (p) comped with pevious theoeticl studies 2, 3 nd expeimentl dt. 4 Method ΔE 1,2 ΔE 1,3 k 1 k 2 k 3 k v (300K) τ v (300K) /Gs t T 1 14 102 6.2E+02 1.0E+05 4.0E+05 1.3E+05 7.5 /Gs t T 1 14 144 1.2E+02 8.3E+03 8.5E+05 1.8E+05 5.6 /COSMO t T 1 11 84 9.8E+02 1.0E+05 5.6E+05 1.8E+05 5.5 /COSMO t T 1 13 105 1.9E+02 1.8E+04 2.0E+06 4.7E+05 2.1 /Gs t S 0 95 95 1.2E+03 1.5E+06 1.5E+06 8.3E+05 1.2 /Gs t S 0 133 133 6.8E+02 1.1E+06 1.1E+06 5.8E+05 1.7 Othe psoc ppoch t T 1,b 17 107 6.7E+02 2.0E+04 3.1E+05 8.2E+04 12.2 Othe psoc ppoch t T 1 b,c 54 69 1.2E+05 1.3E+05 3.2E+05 1.8E+05 5.5 Othe psoc ppoch t S 0 b,c 33 104 2.3E+04 1.5E+06 1.5E+06 9.0E+05 1.1 Exp. d,e 12-12.4 114-135 5.7E+03 5.8E+04 2.9E+06 6.9E+05 1.5 Exp. f,g 13-14 85-150 6.1E+05 h 1.6 h Exp. g,i 19 170 5.6E+05 1.8 3PW91/LnL2DZ(I):D95(est) in condensed phse with n Onsge model; ef 2. b Repoted vlues e coected fo the efctive index of CH 2 Cl 2 (n=1.42) ccoding to the Stickle-eg eltionship. c 3LYP/SDD(I):6-311G*(est) in gs phse; ef 3. d In PMMA; ef 4. e The veged ditive te is clculted by use of the thee individul ditive decy times nd of the zeo-field splitting vlues ccoding to Eq. (1) fo tempetue of 300K. f In THF; ef 4. g The individul ditive tes of the tiplet substtes e not vilble. The veged ditive te is clculted fom the emission quntum yield nd the decy time mesued t mbient tempetue ccoding to Eq. (2). h In 2-MeTHF; ef 4. i In CH 2 Cl 2 ; ef 4. 1 1 e v kv k1 k2e k PL k n k k ( E 1, 2 ( E 1,2 e ( E k e 3 1,3 ( E 1,3 (1) (2) 4
Figue S1. Clculted ZFS (top, in cm -1 ) nd τ (bottom, in s) t the COSMO + level fo sevel I(N^C) 2 (cc) nd Pt(N^C)(cc) compounds, comped to expeimentl dt. 4 5
Figue S2. Clculted ZFS (top, in cm -1 ) nd τ (bottom, in s) t the 4 levels of theoy (petubtive o full SOC, gs phse o COSMO solvtion), comped to expeimentl dt. 4-9 6
Refeences 1 F. Wng nd T. Ziegle, J. Chem. Phys., 2005, 123, 154102. 2 K. Nozki, J. Chin. Chem. Soc., 2006, 53, 101. 3 E. Jnsson,. Minev, S. Schde, H. Ågen, Chem. Phys., 2007, 333, 157. 4 H. Yesin, A. F. Rusch, R. Czewieniec, T. Hofbeck nd T. Fische, Cood. Chem. Rev., 2011, 255, 2622. 7